Fluorinated polymers derived from acrylamide-functional monomers

ABSTRACT

Novel fluorinated, acrylamide monomers are prepared from 2-alkenyl azlactones reacted with fluorinated alcohols. The novel monomers have the formula ##STR1## wherein R 1  and R 6  are independently hydrogen or methyl; R 2  and R 3  independently can be an alkyl, cycloalkyl, or aryl group, or R 2  and R 3  taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms; 
     R 4  and R 5  are independently hydrogen or lower alkyl; 
     a is 0 or 1; 
     b is 1 or 2; 
     X is a single bond, CH 2 , CH 2  OCH 2 , and CH 2  CH 2  OCH 2  ; and 
     R f  is a substantially perfluorinated alkyl, cycloalkyl, or aryl group when b is 1 and perfluorinated alkylene when b is 2. 
     Novel polymers and copolymers can be prepared from the monomers of the invention.

This is a division of application Ser. No. 7/267,186 filed Nov. 4,988now U.S. Pat No. 4,931,582.

Field of the Invention

This invention relates to novel fluorinated, acrylamide-functionalmonomers and a process therefor. In another aspect, this inventionprovides homo- and copolymers of the fluorinated, acrylamide-functionalmonomers. Polymers derived from the novel acrylamide monomers of theinvention find utility, for example, in stain resistant coatings.

BACKGROUND OF THE INVENTION

Substitution of fluorine for hydrogen in polymers and coatings is oftendesirable to impart useful properties such as lower surface energy whichis necessary for stain resistance. Typically, the incorporation offluorine into polymers and coatings has been made by copolymerizing(meth)acrylate monomers derived from (meth)acrylic acid and highlyfluorinated alcohols. These fluorinated (meth)acrylate monomers areavailable commercially from several sources. Despite their generalavailability, however, (meth)acrylates often polymerize at slow ratesand provide polymers which possess inadequate thermal and hydrolyticstabilities.

Fluorinated (meth)acrylamide monomers have been described in severalpatents. U.S. Pat. Nos. 2,743,297; 2,957,914; and 3,997,604 disclosefluorinated (meth)acrylamide monomers prepared by the reaction offluorinated secondary or primary amines and (meth)acryloyl chloride; acomplication in the synthesis is removal of the hydrogen chlorideby-product. U.S. Pat. No. 3,475,434 teaches the reaction of astoichiometric excess (about 300 percent) of a short chain diamine witha perfluorinated acylating agent, isolation and purification of themonoperfluoroamide, and (meth)acryloylation of the remaining aminefunction with the appropriate acid chloride; here again hydrogenchloride is a troublesome by-product, and the complexity of thesynthesis is self-evident. U.S. Pat. No. 3,655,732 teaches a multi-stepsynthesis of fluorinated acrylamides which possess a heteroatom,typically sulfur, as part of a five atom linking group between theacrylamide and perfluorinated moieties.

2 Alkenyl azlactones are known to react with certain nucleophiles suchas primary amines and alcohols to afford (meth)acrylamide-functionalproducts. The interested reader is referred to our recent review articleentitled "Polyazlactones" which is contained in the Encyclopedia ofPolymer Science and Engineering, Volume 11, 2nd edition, 1988. Thereaction product of 2-vinyl-4,4-dimethylazlactone and2,2,2-trifluoroethylamine is a high melting solid (m.p. 135°-136° C.),having been reported by L. D. Taylor, et al., J. Polymer Sci. PolymerLett., 7, 597 (1969). U.S. Pat. No. 4,447,493 discloses the reactionproduct of a 2-alkenyl azlactone and poly(perfluorooxyalkylene) polyols,but these materials contain main chain heteroatoms (oxygen) and oftenyield highly colored reaction products which can be undesirable;additionally, the highly oxygenated, relatively high molecular weightreaction products tend to be less compatible with other necessaryadditives such as monomers, crosslinking agents, and photoinitiators.

SUMMARY OF THE INVENTION

Briefly, the present invention provides novel fluorinated acrylamidemonomers and homo- and copolymers prepared therefrom.

The fluorinated acrylamide monomers are prepared by the reaction of2-alkenyl azlactones and fluorinated alcohols. The reaction isfacilitated by the lack of formation of any product other than thefluorinated acrylamide monomer and is therefore extremely efficaciousfrom a synthesis view point. As expected, the novel acrylamide monomerspolymerize at high rates, and the resulting polymers are environmentallyquite stable. An unexpected and significant benefit observed with theinstant polymers is improved toughness.

In this application:

"acrylamide" and "acrylate" mean both so-called acryloyl, i.e.2-propenoyl, and methacryloyl, i.e., 2-methyl-2-propenoyl, amine andalcohol derivatives;

"substantially perfluorinated" means hydrocarbon groups in which atleast 50 percent of the hydrogen atoms have been replaced by fluorine;

"alkyl" and "alkylene" mean the monovalent and divalent residuesremaining after removal of one and two hydrogen atoms, respectively,from a linear or branched chain hydrocarbon having 1 to 20 carbon atoms;

"lower alkyl" means C₁ to C₄ alkyl;

"aryl" means the monovalent residue remaining after removal of ahydrogen atom from an aromatic compound (single ring and multi- andfused-ring) having 5 to 12 ring atoms and includes substituted aromaticssuch as lower alkaryl and aralkyl, lower C₁ to C₄ alkoxy, N,N-di(loweralkyl)amino, nitro, cyano, halo, and lower alkylcarboxylic ester,wherein "lower" means C₁ to C₄ ;

"azlactone" means 2-oxazolin-5-one groups of Formula I and2-oxazin-6-one groups of Formula II: ##STR2##

"cycloalkyl" means the monovalent residue remaining after removal of ahydrogen atom from a cyclic hydrocarbon having 3 to 12 carbon atoms;

The monomers of the present invention exhibit high rates of free radicalhomo- and copolymerization and yield toughened polymers compared tothose resulting from acrylate- or methacrylate-functional monomers.

a significant advantage of using the 2-alkenyl azlactone as an acylatingagent in the present invention method instead of acryloyl chloride as inthe prior art method is that the azlactone/nucleophile reaction involvesring-opening addition; no smaller by-product molecule (such as hydrogenchloride) is displaced or generated in the reaction.

The acrylamide functionality can offer certain advantages as apolymerizable group over the acrylate. The amide group is known to bemore difficult to hydrolyze than the ester group, and amide-functionalpolymers should therefore be more environmentally stable. Additionally,according to information published in the Polymer Handbook, 2nd edition,edited by J. Brandrup and E. H. Immergut, Wiley-Interscience, New York,1975, pp. II 47-49, acrylamides enjoy rates of free radicalpolymerization substantially faster than corresponding acrylates ormethacrylates. N,N-Dimethylacrylamide, for example, exhibits a rate ofbulk polymerization (k_(p) ² /k_(t)) at 50° C. 1142 times faster thanmethyl acrylate and 457 times faster than methyl methacrylate. Despitethese potential advantages, however, there are presently no fluorinatedacrylamide monomers that are commercially available.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a new class of fluorinated, acrylamidemonomers having the general Formula III: ##STR3##

wherein R¹ and R⁶ are independently hydrogen or methyl;

R² and R³ independently can be an alkyl, cycloalkyl, or aryl group, orR² and R³ taken together with the carbon to which they are joined canform a carbocyclic ring containing 4 to 12 ring atoms;

R⁴ and R⁵ are independently hydrogen or lower alkyl;

a is 0 or 1;

b is 1 or 2;

X is a single bond, CH₂, CH₂ OCH₂, and CH₂ CH₂ OCH₂ ; and

R_(f) is a substantially perfluorinated alkyl, cycloalkyl, or aryl groupwhen b is 1 and perfluorinated alkylene when b is 2.

The novel fluorinated, acrylamide monomers of Formula III are preparedby reaction of 2-alkenyl azlactones having the general Formula IV##STR4## (wherein R¹, R², R³, R⁴, R⁵ and a are as previously defined)with a fluorinated alcohol having the general Formula V: ##STR5##(wherein b, X, R, and R, are as previously defined)

2-Alkenyl azlactones are well-known and their synthesis, physical andchemical properties, homo- and copolymerization behavior, andapplications are discussed in our recent review entitled"Polyazlactones" previously cited. Useful 2-alkenyl azlactones for thepresent invention include 2-vinyl-4,4-dimethyl-2-oxazolin-5-one,2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one,2-vinyl-4-ethyl-4-methyl-2-oxazolin-5-one,2-vinyl-4,4-diethyl-2-oxazolin-5-one,2-vinyl-4-methyl-4-phenyl-2-oxazolin-5-one,2-isopropenyl-4,4-tetramethylene-2-oxazolin-5-one,2-vinyl-4,4-pentamethylene-2-oxazolin-5-one, and2-vinyl-4,4-dimethyl-2-oxazin-6-one.

The preferred 2-alkenyl azlactone because of its reactivity andcommercial availability is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (SNPE,Paris, France). In certain applications that employ radiation curing orphotopolymerization situations in which no solvent is present, however,it is extremely desirable that the fluorinated, acrylamide monomer be aliquid at room temperature or slightly above. In those instances themelting point of the fluorinated, acrylamide monomer product can belowered (relative to R¹ ═H; R² ═R³ ═methyl; and a═0) by utilizing analkenyl azlactone which contains an asymmetric carbon atom at position-4or a six-membered azlactone compound. In those instances,2-vinyl-4-ethyl-4-methyl-2-oxazolin-5-one and2-vinyl-4,4-dimethyl-2-oxazin-6-one are preferred, and references fortheir synthesis are given in our "Polyazlactone" review, supra.

Useful fluorinated alcohols of the present invention which arecommercially available include 1H,1H,7H-dodecafluoro-1-heptanol,perfluorocyclohexyl-1H,1H-methanol,2,2,3,3,4,4,5,5,6,6-decafluoro-1-methylheptanol-1,1H,1H,11H-eicosafluoro-1-undecanol. 1H,1H-heptafluoro-1-butanol,1H,1H,9H-hexadecafluoro-1nonanol, hexafluoroisopropanol,1H,1H,5H-octafluoro-1-pentanol, 1H,1H-pentadecafluorooctanol,pentafluorobenzyl alcohol, 1H,1H-pentafluoropropanol,1H,1H,2H,2H-perfluorodecanol-1, 1H,1H,2H,2H-perfluorodecanol-1,1H,1H,3H-tetrafluoro-1-propanol, 2,2,2-trifluoroethanol,2,2,3,3-tetrafluoro-1,4-butanediol,2,2,3,3,4,4-hexafluoro-1,5-pentanediol, and2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol.

Other fluorinated alcohols useful in the invention, especially when lowmelting acrylamide reaction products are desired are those described inour copending patent application entitled "O-Hydroxyalkylation of1,1-Dihydroperfluorinated Alcohols", U.S. Ser. No. 07/265,035, now U.S.Pat No. 4,942,436, filed the date as this application, which isincorporated herein by reference.

The reaction of the 2-alkenyl azlactone and the fluorinated alcohol isfacilitated by the presence of a catalyst. Useful catalysts include1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene (DBN), triethylamine,1,4-diazabicyclo[2.2.2]octane (DABCO), trioctyphosphine, andtributylphosphine in molar concentrations of from 0.1 to 20 weightpercent, preferably 0.25-5.0 weight percent, and most preferably 0.5-20weight percent based on the azlactone reactant; DBU, DBN, andtrioctylphosphine are preferred. In a typical procedure, equal molarquantities of 2-alkenyl azlactone and fluorinated alcohol are mixed withthe catalyst in the absence of solvent. Alternatively, solvents may beemployed with the provision that they not react with the azlactone orcatalyst under the reaction conditions. Suitable organic solventsinclude ethyl acetate, toluene, tetrahydrofuran, and fluorinatedsolvents such as Freon™ 113 (Du Pont). Especially with the preferredcatalysts and a solvent-free reaction solution, a mildly exothermicreaction will ensue, and the reaction is generally complete asdetermined by infrared spectroscopy when the reaction temperaturereturns to ambient. At this point the fluorinated, acrylamide monomerproduct is either a crystalline solid or a viscous liquid, and for mostpurposes further purification is unnecessary.

With other catalysts and when solvents are employed, warming thereaction mixture will hasten completion of reaction. It is generallyadvisable to add a free radical stabilizer such as phenothiazine or2,6-di-t-butyl p-cresol in concentrations by weight based on reactionproduct of from 0.01 to 1.0 percent, preferrably 0.05-0.15 percent.Suitable warming conditions are from 40°-80° C., preferably 40°-65° C.for a period of 0.5-12 hours, preferably 0.5-2 hours.

As is apparent to one skilled in the art, the fluorinated, acrylamidemonomers of the invention can be polymerized by standard thermally- orphotochemically-initiated free radical addition polymerizationprocedures. Also apparent is that copolymers can be prepared from theinstant monomers and essentially any free radically polymerizable olefinby employing standard techniques. The polymerizations can be effected inthe absence of solvents, if the monomer formulations are liquid at thepolymerization temperatures, or in solution, and several useful,non-reactive solvents have been specified above. Polymers and copolymercan have molecular weights in the range of approximately 20,000 to5,000,000.

Polymers and copolymers of the invention contain structural units ofFormula VI (when b=1) or VII (when b=2), respectively, which are asfollows: ##STR6## wherein R¹, R², R³, R⁴, R⁵, R⁶, R_(F), a, X are aspreviously defined and the open dashes (-) mean an attachment to apolymer main-chain.

An excellent discussion of suitable olefinic monomers for use inpreparing copolymers of the invention is contained in C. E.Schildknecht's text "Vinyl and Related Polymers", Wiley, N.Y., 1959.Examples include: the vinyl aromatic monomers such as styrene,α-methylstyrene, and 2- and 4-vinylpyridine; α, β-unsaturated carboxylicacids such as acrylic acid, methacrylic acid, itaconic acid, maleicacid, fumaric acid, and crotonic acid; α, β-unsaturated carboxylic acidderivatives such as methyl methacrylate, butyl methacrylate,2-ethylhexyl methacrylate, ethyl acrylate, butyl acrylate, isooctylacrylate, octadecyl acrylate, cyclohexyl acrylate, tetrahydrofurfurylacrylate, phenyl acrylate, phenethyl acrylate, benzyl acrylate,cyanoethyl acrylate, diethyl itaconate, acrylamide, acrylonitrile,N,N-dimethylacrylamide, and N-butylacrylamide; vinyl esters ofcarboxylic acids such as vinyl acetate, and vinyl 2-ethylhexanoate;vinyl halides such as vinyl chloride and vinylidene chloride; vinylethers such as methyl vinyl ether, 2-ethylhexyl vinyl ether, and butylvinyl ether; olefins such as ethylene; N-vinyl compounds such asN-vinylpyrrolidone and N-vinylcarbazole; vinyl ketones such as methylvinyl ketone; and vinyl aldehydes such as acrolein and methacrolein. Thepreferred monomers for the purposes of the present invention are the α,β-unsaturated carboxylic acid derivatives.

A surprising feature of the polymers prepared from the fluorinated,acrylamide monomers of the invention is their superior toughness (i.e.at least 25 percent greater) relative to corresponding acrylate polymerswhich contain the same fluorinated group. This is especially surprisingin light of previous work (S. M. Heilmann and H. K. Smith II, J. Appl.Polymer Sci. 24, 1551 (1979)) conducted on pressure sensitive adhesives.In that work it was well established that a secondary amide group(--CONH--) immediately pendant from a polymer main-chain was stericallyincapable of participating in hydrogen bonding between polymer chains(necessary for building cohesion). This was so primarily because of thegroup's immediate proximity to the very large and bulky polymermain-chain. Yet in the present invention, as is exemplified below, thesame immediately pendant secondary amide groups somehow cause asubstantial toughening to occur. While not wishing to be bound by anyexplanation and yet to explain our invention as fully as possible, it isfelt that the toughening effect can be attributed to increased doublebond character of the carbon-nitrogen amide bond. The secondary amidebond functions as a rigid, orientating side group relative to thecarbon-oxygen ester bond in acrylates and, in this fashion, is betterable to absorb and dissipate mechanical stress, thereby exerting atoughening influence.

The fluorinated, acrylamide monomers of the invention intrinsicallypossess low surface energies, as do the polymers and copolymers producedfrom them. The monomers find use as components in stain resistantcoatings for surfaces. One such application as a stain resistant coatingfor fabric is exemplified below.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

EXAMPLE 1 Preparation of 1H,1H,2H,2H-Perfluorodecyl2-Acrylamido-2-methylpropionate

1H,1H,2H,2H-Perfluoro-1-decanol (available from Strem Chemicals, Inc.,Newburyport, MA) (13.28 grams, 0.028 mole) and2-vinyl-4,4-dimethylazlactone (VDM) (available from SNPE, Inc.,Princeton, NJ) (3.98 grams, 0.028 mole) were mixed and warmed to meltthe fluorinated alcohol and facilitate dissolution. To this solutioncooled to room temperature was added 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) (available from Aldrich Chemical Co., Milwaukee, WI) (0.08 gram,0.00056 mole) which caused a warming of the reaction solution to about40° C. When the reaction solution had cooled to room temperature, aninfrared spectrum showed characteristic absorptions for the acrylamideproduct: 3.05 (NH stretch), 5.75 (ester C═0), 6.05 (amide C═0), 6.15(C═C), and 6.50 (amide II) microns. Upon standing overnight, thereaction product crystallized and melted at 30°-35° C.

EXAMPLES 2-23

Employing the procedure of EXAMPLE 1, several fluorinated acrylamidemonomers of Formula III which possess the specific structures indicatedin Table 1 were prepared.

                                      TABLE I                                     __________________________________________________________________________     ##STR7##                                   III                               Example                                                                            R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          a R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                          X     b R.sub.f  m.p. (°C.).sup.a               __________________________________________________________________________     2   H  Me.sup.f                                                                         Me 0 --                                                                              --                                                                              H  sb.sup.d                                                                            1 CF.sub.3 (CF.sub.2).sub.2                                                              45                                     3   Me Ph.sup.g                                                                         Ph 0 --                                                                              --                                                                              H  sb    1 CF.sub.3 (CF.sub.2).sub.2                                                              79                                     4   H  Me Me 0 --                                                                              --                                                                              H  sb    1 H(CF.sub.2).sub.4                                                                      48                                     5   H  Me Me 0 --                                                                              --                                                                              H  sb    1 H(CF.sub.2).sub.4                                                                      52                                     .sup. 6.sup.e                                                                     H  Me Me 0 --                                                                              --                                                                              H  sb    1 CF.sub.3 (CF.sub.2).sub.6                                                              53                                     7   H  Me Me 0 --                                                                              --                                                                              Me CH.sub.2 OCH.sub.2                                                                  1 CF.sub.3 (CF.sub.2).sub.6                                                              <22                                    8   H  Me Me 0 --                                                                              --                                                                              H  sb    1 c-C.sub.6 F.sub.11                                                                     99                                     9   H  Me Me 0 --                                                                              --                                                                              H  CH.sub.2                                                                            1 NSO.sub.2 (CF.sub.2).sub.7 CF.sub.3                                                    103                                                                  Et                                             10   H  Me Et.sup.h                                                                         0 --                                                                              --                                                                              H  sb    1 CF.sub.3 (CF.sub.2).sub.6                                                              <22                                   11   H  Me Me 1 H H H  sb    1 CF.sub.3 (CF.sub.2).sub.6                                                              <22                                   12   H  Me Me 0 --                                                                              --                                                                              H  CH.sub.2 OCH.sub.2                                                                  1 CF.sub.3 (CF.sub.2).sub.6                                                              <22                                   13   Me Me Me 0 --                                                                              --                                                                              H  sb    1 CF.sub.3 (CF.sub.2).sub.6                                                              72                                    14   H  Me Me 0 --                                                                              --                                                                              H  sb    2 (CF.sub.2).sub.4                                                                       145                                   15   H  Me Et 0 --                                                                              --                                                                              H  sb    2 (CF.sub.2).sub.4                                                                       146                                   16   H  Me Et 0 --                                                                              --                                                                              H  sb    2 (CF.sub.2).sub.3                                                                       95                                    17   H  Me Et 0 --                                                                              --                                                                              H  sb    2 (CF.sub.2).sub.2                                                                       151                                   18   H  Me Et 0 --                                                                              --                                                                              H  CH.sub.2                                                                            1 CF.sub.3 (CF.sub.2).sub.7                                                              <22                                   19   H  Me Me 1 H H H  CH.sub.2                                                                            1 CF.sub.3 (CF.sub.2).sub.7                                                              25                                    20   H  Me Me 1 H H H  sb    2 (CF.sub.2).sub.2                                                                       105                                   21   H  Me Me 1 H H H  sb    2 (CF.sub.2).sub.3                                                                       <22                                   22   H  Me Me 1 H H H  sb    1 H(CF.sub.2).sub.6                                                                      <22                                   23   H  Me Et 0 --                                                                              --                                                                              H  sb    1 H(CF.sub.2).sub.6                                                                      <22                                   __________________________________________________________________________     .sup.a Melt temperatures were measured on unrecrystallized samples. The       upper temperature of the melting range is recorded at which a clear melt      is present.                                                                   .sup.d sb means single bond                                                   .sup.e This Example was conducted using trioctylphosphine (2 mol %)           instead of DBU as catalyst.                                                   .sup.f Me = Methyl                                                            .sup.g Ph = phenyl                                                            .sup.h Et = ethyl                                                        

EXAMPLE 24

This example illustrates the improved toughness observed in polymersprepared with the novel fluorinated, acrylamide monomers of theinvention compared to corresponding poly(acrylates).

The fluorinated, acrylamide monomer of Example 6 containing 0.5 weightpercent of a photoinitiator (Darocur™ 1116, Merck, Darmstadt, WestGermany) was coated onto a silicone treated paper backing at a thicknessof 1.9 mm (75 mils). The coating was exposed to a lamp emittingradiation with wavelengths between 300 and 400 nm (Blacklight™,Sylvania) in a nitrogen atmosphere for 30 minutes. 1,1Dihydroperfluorooctyl acrylate (Monomer Polymer & Dajac, Trevose, PA)(viscosity about 1 cps) and the Darocur were irradiated in bulk in aPyrex® vessel with Blacklight to obtain a thickened coatable syrup(viscosity about 1500 cps). This syrup was then coated at 1.9 mm (75mils) and polymerized as described above. The stress-strainrelationships of 1.27 cm (0.5 inch) wide samples of the two non-tacky,conformable polymer films were recorded using a Universal Test Machine(available from Instron Corp., Canton, MA; crosshead rate: 2 cm/min).The poly(fluorinated, acrylamide monomer) exhibited a toughness (atYield) of 3313 cm-g/mL (47 in-lbs/in-³), while thepoly(1,1-dihydroperfluorooctyl acrylate) gave a toughness value of 2115cm-g/mL (30 in-lbs/in³).

EXAMPLE 25

This example teaches the use of a fluorinated, acrylamide monomer of theinvention in a stain resistant preparation for fabrics.

Preparation of the Stain Resistant Polymer Charge:

    ______________________________________                                        1H,1H,2H,2H-perfluorodecyl                                                                            13.89 grams                                           2-acrylamido-2-methylpropionate (Example 1)                                   n-butyl acrylate         7.48 grams                                           1,1,1-trichloroethane   49.86 grams                                           azobis(iso-butyronitrile)                                                                              0.11 grams                                           ______________________________________                                    

The charge solution was degassed briefly with nitrogen in a four ouncebottle. The bottle was sealed and heated with agitation at 55° C. for 22hours. At that point the copolymer solution was clear and very viscous;the copolymer weight percent solids was 29.2 percent, indicating greaterthan 97 percent conversion of monomers to copolymer.

Evaluation of the Stain Resistance of the Copolymer

A portion of the above copolymer solution was diluted with additional1,1,1-trichloroethane to 0.7 percent solids. The stain resistantproperties of the instant copolymer were compared both to untreatedfabrics and fabrics treated in analogous fashion with 3M's SCOTCHGARDfabric protector. The evaluation procedure was that reported by C. L.Steel, Book Pap.-Int. Conf. Exhib., AATCC. 237-247 (1986). The fabricsevaluated and results obtained are shown in TABLE II below:

                  TABLE II                                                        ______________________________________                                        Fabric Number   Description                                                   ______________________________________                                        1               rayon face velvet - lt. green                                 2               nylon flat upholstery - ready                                                 for printing, scoured and                                                     rubberized                                                    3               100% cotton woven print                                       4               nylon taffeta, lt. wt. single                                                 ply, uncoated                                                 5               12 oz. wool woven worsted                                                     gabardine, off-white,                                         6               cotton sheeting - white,                                                      bleached, and mercerized                                      ______________________________________                                        Fabric                                                                              Oil.sup.e                                                                              Water.sup.f                                                                           Spray.sup.g                                                                            Abrasion.sup.h                                                                        Soil.sup.i                            ______________________________________                                        UNTREATED RESULTS:                                                            1     0        0       0        0       3                                     2     0        0       0        0       2                                     3     0        0       0        0       3                                     4     0        0       0        0       3                                     5     0        1       70       0       2                                     6     0        0       0        0       2.5                                   EXAMPLE 25 RESULTS:                                                           1     5        6       70       2       3                                     2     4        6       70       3       1.5                                   3     3        4       80       2       2.5                                   4     3        5       70       2       2.5                                   5     6        6       100      2       2.5                                   6     2        5       80       2       1.5                                   SCOTCHGARD RESULTS:                                                           1     5        7       70       2       3.5                                   2     5        5       80       5       2.5                                   3     6        8       80       5       4                                     4     4        5       70       3       3                                     5     6        8       100      3       2.5                                   6     5        4       70       4       3                                     ______________________________________                                         .sup.e oil repellency: scale 0-8: 8 = best                                    .sup.f water/alcohol resistance: scale F-10: 10 = best                        .sup.g spray rating: scale 0-100: 100 = best                                  .sup.h abrasion resistance scale 0-8: 8 = best                           

The above results with the various fabrics and stain preparationsindicate that the copolymer of Example 25 is far superior to notreatment and compares favorably with a commercial fabric protectionproduct.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodimentsset forth herein.

We claim:
 1. A polymer comprising units having at least one of theformulae ##STR8## ##STR9## where R¹ and R⁶ are independently hydrogen ormethyl;R² and R³ independently are alkyl, cycloalkyl, or aryl group, orR² and R³ taken together with the carbon to which they are form acarbocylic ring containing 4 to 12 ring atoms; R⁴ and R⁵ areindependently hydrogen or lower alkyl; a is 0 or 1; [b is 1 or 2]; X isa single bond, CH₂, CH₂ OCH₂, or CH₂ CH₂ OCH₂ ; and R_(F) is an alkyl,cycloalkyl, or aryl group in Formula VI and alkylene in Formula VII,wherein at least 50 percent of the hydrogen atoms have been replaced byfluorine, and the open dashes (-) mean attachment to a polymermain-chain.
 2. The polymer according to claim 1 further comprising unitsderived from at least one copolymerizable olefin.
 3. The polymeraccording to claim 1 wherein R¹ is hydrogen.
 4. The polymer according toclaim 1 wherein R² and R³ are independently lower alkyl of 1 to 4 carbonatoms.
 5. The polymer according to claim 1 wherein R⁶ is hydrogen. 6.The polymer according to claim 1 wherein a is 1 and R⁴ and R⁵ arehydrogen.
 7. The polymer according to claim 1 which is a homopolymer..Iadd.8. A polymer comprising units having the formula##STR10##.Iaddend. whereR¹ and R⁶ are independently hydrogen or methyl;R² and R³ independently are alkyl, cycloalkyl, or aryl group, or R² andR³ taken together with the carbon to which they are formed form acarbocyclic ring containing 4 to 12 ring atoms; R⁴ and R⁵ areindependently hydrogen or lower alkyl; a is 0 or 1; X is a single bond,CH₂, CH₂ OCH₂, or CH₂ CH₂ OCH₂, and R_(F) is ##STR11## .Iadd.9. Thepolymer according to claim 8 wherein R¹ is H,R² is CH₃, R³ is CH₃, a is0, R⁶ is H, X is CH₂, and ##STR12##.Iaddend.